System and method for determining state of charge for an electric energy storage device

ABSTRACT

Systems and methods for operating an electric energy storage device are described. The systems and methods may generate a state of charge estimate that is based on negative electrode plating. An overall state of charge may be determined from the state of charge estimate that is based on negative electrode plating and a state of charge estimate that is not based on negative electrode plating.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 16/179,665 entitled “System and Method for Determining State ofCharge for an Electric Energy Storage Device”, filed on Nov. 2, 2018.

FIELD

The present description relates to a system and method for determiningstate of charge of an electric energy storage device. The methods andsystems may be particularly useful for electrical power systems thatinclude two electrolytes that are not in fluidic communication.

BACKGROUND AND SUMMARY

An oxidation-reduction flow battery may store electrical power that hasbeen generated via an array of photovoltaic cells, wind turbines,hydroelectric generators, or other sources so that the electrical powermay be delivered to electrical loads at a later time when output of theelectrical power source may be low or when electrical loads are high.The oxidation-reduction flow battery stores electrical energy inchemical form in electrolyte and it also converts chemical energy intoelectrical energy via redox reactions that include the electrolyte.Because electric energy is stored in the electrolyte, the electricenergy storage capacity of the oxidation-reduction flow battery may bechanged by simply changing the volume of electrolyte stored within theoxidation-reduction flow battery. In addition, the total charge storagecapacity of the oxidation-reduction flow battery may be determined fromthe volume of electrolyte in the oxidation-reduction flow batterysystem.

Electric energy storage system design requirements may be the basis forsetting the total charge storage capacity of an oxidation-reduction flowbattery, but it may also be desirable to determine a state of charge(SOC) for the oxidation-reduction flow battery. The SOC may be describedas a ratio of an amount of electric charge stored in an electric energystorage device (e.g., an oxidation-reduction flow battery) to the fullor total theoretical amount of electric charge that may be stored in theelectric energy storage device. The SOC may be useful to decide whencharging of an oxidation-reduction flow battery should be stopped orstarted. Further, the SOC may be useful to determine maximum rates ofcharging and discharging power for the oxidation-reduction flow batteryat different SOC levels.

One way to estimate SOC for an oxidation-reduction flow battery is tomeasure positive electrolyte oxidation/reduction potential (ORP) as anindication of Fe³⁺ ions in positive electrolyte as a measure of SOC.However, measuring ORP of positive electrolyte may not be as accurate asmay be desired to determine SOC because negative electrode sidereactions may offset the overall battery storage capacity from thepositive state of charge. Therefore, it may be desirable to provide away of determining SOC that takes into consideration negative sidereactions and that better matches the actual battery storage capacity.

The inventors herein have recognized the above-mentioned issues and havedeveloped a method for determining state of charge of an electric energystorage device, comprising: adjusting operation of an electric energystorage device via a controller according to a state of charge of theelectric energy storage device, the state of charge generated via aplating efficiency of the electric energy storage device and a currentflow of the electric energy storage device.

By determining a plating efficiency of an electric energy storagedevice, it may be possible to improve state of charge estimates for anoxidation-reduction flow battery. In particular, plating efficiency atthe negative electrode may be indicative of a battery's capacity tosource and sink current and the plating efficiency values may relate toside reactions at the negative electrode. As such, the platingefficiency may be useful to count coulombs entering and exiting anoxidation-reduction flow battery and to determine a SOC estimate for anoxidation-reduction flow battery.

The present description may provide several advantages. In particular,the approach may improve SOC estimates for an oxidation-reduction flowbattery. Further, the approach may be useful to improve control of anoxidation-reduction flow battery. In addition, the approach may beuseful to determine when it may be desirable to perform anoxidation-reduction flow battery cleansing procedure to improve batterycell efficiency.

The above advantages and other advantages, and features of the presentdescription will be readily apparent from the following DetailedDescription when taken alone or in connection with the accompanyingdrawings.

It should be understood that the summary above is provided to introducein simplified form a selection of concepts that are further described inthe detailed description. It is not meant to identify key or essentialfeatures of the claimed subject matter, the scope of which is defineduniquely by the claims that follow the detailed description.Furthermore, the claimed subject matter is not limited toimplementations that solve any disadvantages noted above or in any partof this disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

The advantages described herein will be more fully understood by readingan example of an embodiment, referred to herein as the DetailedDescription, when taken alone or with reference to the drawings, where:

FIG. 1A is a schematic diagram showing a single cell of an electricpower storage and delivery system;

FIGS. 1B and 1C show schematics representations of charging anddischarging reactions for an oxidation-reduction flow battery.

FIG. 2 is a schematic diagram of an electric power system that includesa plurality of cells;

FIG. 3 shows an example plot of pH versus negative electrode platingefficiency;

FIG. 4 shows an example plot of SOC versus open circuit voltage; and

FIG. 5 shows a flowchart of an example method for determining SOC andapplying results of a SOC estimate.

DETAILED DESCRIPTION

The present description is related to estimating state of charge (SOC)for an oxidation-reduction flow battery. One cell of anoxidation-reduction flow battery is shown in FIG. 1A. FIGS. 1B and 1Cgraphically illustrate chemical reactions that may occur within anoxidation-reduction flow battery cell shown in FIG. 1A. A plurality ofoxidation-reduction flow battery cells may be arranged in series andparallel as shown in FIG. 2 to form an electric energy storage system.The electric energy storage system may communicate SOC values toexternal controllers so that external electric power sources andconsumers may work efficiently with the electric energy storage system.A plot of electrolyte pH versus negative electrode plating efficiency isshown in FIG. 3 . The relationship shown in FIG. 3 may be applied toestimate SOC of an oxidation-reduction flow battery. FIG. 4 shows a plotof SOC versus open circuit voltage (OCV). The relationship shown in FIG.4 may be applied to verify estimates of SOC that are based on negativeelectrode plating efficiency. A method to determine SOC via negativeelectrode plating efficiency is shown in FIG. 5 .

Referring to FIG. 1A, an example of an all iron redox flow battery (IFB)cell is shown. The IFB cell 175 is an electric energy storage device. Ina redox flow battery system the negative electrode 114 may be referredto as the plating electrode and the positive electrode 116 may bereferred to as the redox electrode. The negative electrolyte within theplating side (e.g., negative reactor 122) of the battery cell may bereferred to as the plating electrolyte and the positive electrolyte onthe redox side (e.g. positive reactor 124) of the battery may bereferred to as the redox electrolyte.

The IFB cell may be supplied with plating electrolyte (e.g., FeCl₂,FeCl₃, FeSO₄, Fe₂(SO₄)₃, and the like)) that is stored in platingelectrolyte tank 100. The IFB may also include redox electrolyte that isstored in redox electrolyte tank 101. The plating electrolyte and redoxelectrolyte may be a suitable salt dissolved in water, such as FeCl₂,FeCl₃, FeSO₄, Fe₂(SO₄)₃, and the like). Both the plating electrolyte andredox electrolyte may use the same salt at different molarconcentrations, a feature of the IFB not available in batteries withdifferent reactive compounds. Tank 100 may be in fluidic communicationwith negative reactor 122. Tank 101 may be in fluidic communication withpositive reactor 124. Electrolyte in tank 100 and negative reactor 122is in fluidic isolation from electrolyte in tank 101 and positivereactor 124. Separating the negative and positive reactors is barrier120, which may comprise an electrically insulating ionic conductingbarrier which prevents bulk mixing of the positive electrolyte and thenegative electrolyte while allowing conductance of specific ions therethrough. The barrier 120 may be embodied as a membrane barrier, such asan ion exchange membrane or a microporous membrane, placed between theplating electrolyte and redox electrolyte to reduce electrolytecross-over and provide ionic conductivity. The IFB cell 175 may furtherinclude negative battery terminal 22, and positive battery terminal 24for supplying current to the IFB cell 175 during charging and fordrawing current from the IFB cell 175 during discharging.

Sensors 102 and 104 may be used to determine the chemical properties ofthe electrolyte, including pH and may be embodied as an optical sensor.Probes 126 and 128 may additionally or alternatively be used todetermine the chemical properties (discussed below) of the electrolytes.Other examples may have a plating electrolyte probe, plating electrolytesensor, redox electrolyte probe, redox electrolyte sensor, or somecombination thereof. The probe may also be placed inside the reactingportion of the IFB in negative reactor 122 and positive reactor 124. Anacid additive may be stored in additional tanks 106 and 108. These maycontain different additives and be controlled by different routines. Inother examples, the IFB may also have either a positive side additive ora negative side additive and not both. The positive side additive may beaccelerated into the positive reactor 124 by positive additive pump 112,the negative additive may be accelerated into the negative reactor 122by negative additive pump 110. Alternately, the electrolyte additivesmay be pumped into tanks 100 and 101. Pumps 110 and 112 may be actuatedvia a control system 150 communicatively coupled to the pumps. Thecontrol system may be responsive to probe 126, probe 128, sensor 102,sensor 104, or any combination thereof. Electrolyte may be pumped to orfrom the negative reactor 122 by pump 131. Electrolyte may be pumped toor from the positive reactor 125 via pump 130. The IFB includes anegative electrode 114 and a positive electrode 116.

Control system 150 may include inputs and outputs 154 (e.g., digitalinputs, digital outputs, analog inputs, analog outputs, pulse widthoutputs, etc.), a central processor 152, random-access memory 155, andread-only (e.g., non-transitory memory) 156. Control system 150 mayreceive data from the various sensors and actuators shown in FIGS. 1Aand 2 . Further, control system 150 may adjust the actuators of FIGS. 1Aand 2 to alter states of devices and electrolyte in the physical world.Control system 150 may receive data and instructions from human/machineinterface 151 (e.g., display panel, keyboard, pushbuttons, etc.).Further, control system 150 may send data to human/machine interface 151and external controller 250.

During normal operation (e.g., not during a cleansing cycle), firstthree-way valve 170 prevents flow of plating electrolyte through bypasspassage 180 and permits flow of plating electrolyte from negativereactor 122 to pump 131 as indicated by arrow 177. Similarly, duringnormal operation, second three-way valve 171 prevents flow of redoxelectrolyte through bypass passage 181 and permits flow of redoxelectrolyte from positive reactor 124 to pump 130 as indicated by arrow178. Thus, plating electrolyte is separated and isolated from redoxelectrolyte.

During a cleansing cycle, it may be desirable to mix plating electrolytewith redox electrolyte. The mixing may be accomplished via positioningfirst three-way valve 170 and second three-way valve 171 to secondpositions. While operating in their second positions, first valve 170permits plating electrolyte to flow through bypass passage 180 asindicated by arrow 172 and prevents plating electrolyte from flowingfrom negative reactor 122 to pump 131. Similarly, while in a secondposition, second valve 171 permits plating electrolyte to flow throughbypass passage 181 as indicated by arrow 173 and prevents platingelectrolyte from flowing from positive reactor 124 to pump 130. Valves170 and 171 may be adjusted between first and second positions viacontroller 150.

Referring now to FIGS. 1B and 1C, graphic representations ofelectrochemical reactions that may take place in an electric energystorage device such as the IFB cell 175 of the electric power andstorage delivery system of FIG. 1A is shown. For example, FIGS. 1B and1C depict the electrochemical reactions occurring at or in the vicinityof the negative electrode 114 (in the negative reactor 122) and positiveelectrode 116 (in the positive reactor 124) of IFB cell 175.

As illustrated in FIG. 1B, ferrous ion, Fe²⁺ receives two electrons andplates as iron metal on to the negative electrode 114 via a platingreaction, while at the positive electrode 116, Fe²⁺ loses an electron toform ferric ion, Fe³⁺, during charging. In contrast, as shown in FIG.1C, iron metal, Fe⁰ at the negative electrode 114 loses two electronsand re-dissolves as Fe²⁺ during discharging, while at the positiveelectrode 116, Fe³⁺ gains an electron to form Fe²⁺. The electrochemicalreactions are summarized in chemical equations (1) and (2), wherein theforward reactions (left to right) indicate electrochemical reactionsduring charging, while the reverse reactions (right to left) indicateelectrochemical reactions during discharging:Fe²⁺+2e⁻↔Fe⁰−0.44 V(Negative Electrode)  (1)2Fe²⁺↔2Fe³⁺+2e⁻+0.77 V(Positive Electrode)  (2)

The negative electrolyte supplied to the IFB cell 175 may provide asufficient amount of Fe²⁺ so that, during charge, Fe²⁺ can accept twoelectrons from the negative electrode to form Fe⁰ and plate onto asubstrate. During discharging, the plated Fe⁰ may then lose twoelectrons, ionizing into Fe²⁺ and be dissolved back into theelectrolyte. The equilibrium potential of the above reaction is −0.44Vand thus this reaction provides a negative terminal for the desiredsystem. On the positive side of the IFB cell 175, the electrolyte mayprovide Fe²⁺ during charging which loses electron and oxidizes to Fe³⁺.During discharging, Fe³⁺ provided by the electrolyte becomes Fe²⁺ byabsorbing an electron provided by the electrode. The equilibriumpotential of this reaction is +0.77V, creating a positive terminal forthe desired system.

Charging is achieved by applying a current across the electrodes vianegative and positive terminals 22 and 24. The negative electrode 114may be coupled via negative terminal 22 to the negative side of avoltage source so that electrons may be delivered to the negativeelectrolyte via the positive electrode 116 (e.g., as Fe²⁺ is oxidized toFe³⁺ in the positive electrolyte in the positive reactor 124). Theelectrons provided to the negative electrode 114 (e.g., platingelectrode) can reduce the Fe²⁺ in the negative electrolyte to form Fe⁰at the plating substrate causing it to plate onto the negative electrode114.

Discharging can be sustained while Fe⁰ remains available to the negativeelectrolyte for oxidation and while Fe³⁺ remains available in thepositive electrolyte for reduction. As an example, Fe³⁺ availability canbe maintained by increasing the concentration or the volume of thepositive electrolyte to the positive reactor 124 to provide additionalFe³⁺ ions via redox electrolyte tank 101. More commonly, availability ofFe⁰ during discharge may be an issue in IFB systems, wherein the Fe⁰available for discharge may be proportional to the surface area andvolume of the negative electrode substrate as well as the platingefficiency. Charging capacity may be dependent on the availability ofFe²⁺ in the negative reactor 122. As an example, Fe²⁺ availability canbe maintained by providing additional Fe²⁺ ions via plating electrolytetank 100 to increase the concentration or the volume of the negativeelectrolyte to the negative reactor 122.

In an IFB, the positive electrolyte comprises ferrous ion, ferric ion,ferric complexes, or any combination thereof, while the negativeelectrolyte comprises ferrous ion or ferrous complexes, depending on thestate of charge of the IFB system. Utilization of iron ions in both thenegative electrolyte and the positive electrolyte allows for utilizationof the same electrolytic species on both sides of the battery cell,which can reduce electrolyte cross-contamination and can increase theefficiency of the IFB system, resulting in less electrolyte replacementas compared to other redox flow battery systems.

Efficiency losses in an IFB may result from electrolyte crossoverthrough the barrier 120 (e.g., ion-exchange membrane barrier,micro-porous membrane, and the like). For example, ferric ions in thepositive electrolyte may be driven toward the negative electrolyte by aferric ion concentration gradient and an electrophoretic force acrossthe barrier 120. Subsequently, ferric ions penetrating the barrier 120and crossing over to the negative reactor 122 may result in coulombicefficiency losses. Ferric ions crossing over from the low pH redox side(e.g., more acidic positive reactor 124) to high pH plating side (e.g.,less acidic negative reactor 122) can result in precipitation ofFe(OH)₃. Precipitation of Fe(OH)₃ can damage the barrier 120 and causepermanent IFB cell performance and efficiency losses. For example,Fe(OH)₃ precipitate may chemically foul the organic functional group ofan ion-exchange membrane or physically clog the small micro-pores of anion-exchange membrane. In either case, due to the Fe(OH)₃ precipitate,ohmic resistance across the barrier 120 may rise over time and batteryperformance may degrade.

Additional coulombic efficiency losses may be caused by reduction of H⁺(e.g., protons) and subsequent formation of H₂ (e.g., hydrogen gas), andthe reaction of protons in the negative reactor 122 with electronssupplied at the plated iron metal electrode 114 to form hydrogen gas.

The IFB electrolyte (e.g., FeCl₂, FeCl₃, FeSO₄, Fe₂(SO₄)₃, and the like)is readily available and can be produced at low costs. The IFBelectrolyte offers higher reclamation value because the same electrolytecan be used for the negative electrolyte and the positive electrolyte,consequently reducing cross contamination issues as compared to othersystems. Furthermore, owing to its electron configuration, iron maysolidify into a generally uniform solid structure during plating thereofon the negative electrode substrate. For zinc and other metals commonlyused in hybrid redox batteries, solid dendritic structures may formduring plating. The stable electrode morphology of the IFB system mayincrease the efficiency of the battery in comparison to other redox flowbatteries. Further still, iron redox flow batteries reduce the use oftoxic raw materials and can operate at a relatively neutral pH ascompared to other redox flow battery electrolytes. Accordingly, IFBsystems reduce environmental hazards as compared with all other currentadvanced redox flow battery systems in production.

During charge of an IFB, for example, ferrous ion, Fe²⁺, is reduced(accepts two electrons in a redox reaction) to metal iron, Fe⁰, at thenegative electrode. Simultaneously, at the positive electrode, ferrousion, Fe²⁺, is oxidized (loss of an electron) to ferric ion, Fe³⁺.Concurrently, at the negative electrode, the ferrous iron reductionreaction competes with the reduction of protons, H⁺, wherein two protonseach accept a single electron to form hydrogen gas, H₂ and the corrosionof iron metal to produce ferrous ion, Fe²⁺. The production of hydrogengas through reduction of hydrogen protons and the corrosion of ironmetal are shown in chemical equations (3) and (4), respectively:

$\begin{matrix}\begin{matrix}\left. {H^{+} + e^{-}}\leftrightarrow{\frac{1}{2}H_{2}} \right. & \left( {{proton}{reduction}} \right)\end{matrix} & (3)\end{matrix}$ $\begin{matrix}\begin{matrix}\left. {{Fe^{0}} + {2H^{+}}}\leftrightarrow{{Fe^{2 +}} + H_{2}} \right. & \left( {{iron}{corrosion}} \right)\end{matrix} & (4)\end{matrix}$

As a result, the negative electrolyte in the negative reactor 122 tendsto stabilize at a pH range between 3 and 6. At the positive reactor 124,ferric ion, Fe³⁺, has a much lower acid disassociation constant (pKa)than that of ferrous ion, Fe²⁺. Therefore, as more ferrous ions areoxidized to ferric ions, the positive electrolyte tends to stabilize ata pH less than 2, in particular at a pH closer to 1.

Accordingly, maintaining the positive electrolyte pH in a first range inwhich the positive electrolyte (positive reactor 124) remains stable andmaintaining the negative electrolyte pH in a second range in which thenegative electrolyte (negative reactor 122) remains stable may reducelow cycling performance and increase efficiency of redox flow batteries.For example, maintaining a pH of a negative electrolyte in an IFB cellbetween 3 and 4 may reduce iron corrosion reactions and increase ironplating efficiency, while maintaining a pH of a positive electrolyteless than 2, in particular less than 1, may promote the ferric/ferrousion redox reaction and reduce ferric hydroxide formation.

As indicated by chemical equations (3) and (4), evolution of hydrogencan cause electrolyte imbalance in a redox flow battery system. Forexample, during charge, electrons flowing from the positive electrode tothe negative electrode (e.g., as a result of ferrous ion oxidation), maybe consumed by hydrogen evolution via chemical equation (3), therebyreducing the electrons available for plating given by chemical equation(1). Because of the reduced plating, battery charge capacity is reduced.Additionally, corrosion of the iron metal further reduces batterycapacity since a decreased amount of iron metal is available for batterydischarge. Thus, an imbalanced electrolyte state of charge between thepositive reactor 124 and the negative reactor 122 can develop as aresult of hydrogen production via chemical reactions (3) and (4).Furthermore, hydrogen gas production resulting from iron metal corrosionand proton reduction both consume protons, which can result in a pHincrease of the negative electrolyte. As discussed above, an increase inpH may destabilize the electrolyte in the redox batter flow system,resulting in further battery capacity and efficiency losses.

Referring now to FIG. 2 , a schematic block diagram of an electric powersystem 200 that includes a plurality of the IFB cells 175 a-175 x andcontroller 150. Controller 150 may read voltage levels of electricenergy storage cell stacks 240-246 and current flow through electricenergy storage cell stacks 240-246 via sensors 210. Controller 150 mayalso selectively operate contactors 225-228 and main contactor 277.Controller 150 may communicate data (e.g., SOC values) to externalcontroller 250 via network (e.g., local area network (LAN), controllerarea network (CAN), or other known network) so that external controller250 may operate external electric power consumers 278 and sources 279 inconjunction with operation of electric energy storage system 200.Electric power system 200 includes all of the components shown in FIG.1A.

IFB cells 175 a-175 x are the same as cell 175 shown in FIG. 1A. Theletter designations are provided simply to identify individual electricenergy storage cells. IFB cells 175 a-175 f are arranged in a first cellstack 240. IFB cells 175 g-175 l are arranged in a second cell stack242. IFB cells 175 m-175 r are arranged in a third cell stack 244. IFBcells 175 s-175 x are arranged in a fourth cell stack 246. Although FIG.2 shows four cell stacks in electric energy storage system 200, electricenergy storage system 200 is not limited to four electric energy storagecell stacks. Rather, electric energy storage system 200 may include from1 to N electric energy storage cell stacks, where N is an integernumber. Further, each electric energy storage cell stack shown in FIG. 2includes six electric energy storage cells (e.g., 175 a-175 f). However,electric energy storage system 200 is not limited to six electric energystorage cells in each electric energy storage cell stacks. Rather,electric energy storage system 200 may include from 1 to M electricenergy storage cells in an electric energy storage cell stack, where Mis an integer number. Each of electric energy storage cells 175 a-175 xincludes a positive side 116 and a negative side 114.

Each electric energy storage cell stacks 201-204 includes a contactor220-223 for selectively individually coupling and decoupling electricenergy storage cell stacks 201-204 to electric power conductor or bus260. Contactor 225 includes a first side 225 a, which is directlycoupled to electric power conductor 260, and a second side 225 b, whichis directly coupled to electric energy storage cell stack 240. Likewise,contactors 226-228 include first sides 226 a-228 a, which are directlycoupled to electric power conductor 260, and second sides 226 b-228 b,which are directly coupled to electric energy storage cell stacks242-246. Contactors 225-228 may be open (e.g., not allowing current toflow through the contactor) when electric energy storage system 200 isdeactivated. Further, contactors 225-228 may be individually opened andclosed (e.g., allowing current flow through the contactor) toselectively electrically isolate selected electric energy storage cellstacks 240-246 from electric power conductor 260 when one or more ofelectric energy storage cells 175 a-175 x are cleansed. Contactors225-228 may be selectively opened and closed via controller 150.

Electric energy storage cell stack 240 may be solely discharged toelectric power consumer via closing contactor 225, closing maincontactor 277, and opening contactors 226-228. Likewise, electric energystorage cell stacks 242-246 may be solely charged or discharged viaclosing one of contactors 226-228, closing main contactor 277, andopening the other contactors 226-228.

Electric energy storage system 200 also includes a main contactor 277that may be opened and closed via controller 150. Main contactor 277 maybe closed to electrically couple electric power conductor 260 toexternal electric energy sources (e.g., photovoltaic cells, windturbines, hydroelectric generators, etc.) 279 and electrical energyconsumers (e.g., house hold appliances, industrial motors, vehiclepropulsion sources, etc.) 278. Main contactor 277 may be opened toelectrically isolate IFB cell electric energy power conductor 260 fromelectrical energy sources 279 and electrical energy consumers 278.Electrical energy sources 279 and electrical energy consumers 278 areexternal to electric energy storage system 200.

Thus, the system of FIGS. 1A and 2 provides for an electric powersystem, comprising: an iron flow electric energy storage cell stackincluding a positive electrode and a negative electrode, the positiveelectrode in physical communication with a first electrolyte (e.g.,redox electrolyte) and the negative electrode in physical communicationwith a second electrolyte (e.g., plating electrolyte); and a controllerincluding executable instructions stored in non-transitory memory togenerate a first state of charge via a plating efficiency and togenerate a second state of charge from other than the platingefficiency, and instructions to generate a charging state of charge viaselecting a greater of the first state of charge and the second state ofcharge during charging of the iron flow electric energy storage cell.The electric power system further comprises additional instructions togenerate a discharging state of charge via selecting a lesser of thefirst state of charge and the second state of charge during dischargingof the iron flow electric energy storage cell. The electric power systemfurther comprises additional instructions to multiply the platingefficiency and current of the iron flow electric energy storage cellstack. The electric power system further comprises additionalinstructions to generate a correction factor from the charging state ofcharge and an open circuit state of charge estimate. The electric powersystem further comprises additional instructions to multiply thecorrection factor and the charging state of charge. The electric powersystem includes where the iron flow electric energy storage cell stackincludes a membrane that physically separates and isolates the firstelectrolyte from the second electrolyte.

Referring now to FIG. 3 , a plot 300 that illustrates an examplerelationship between plating electrolyte pH and negative electrodeplating efficiency is shown. The plot represents a function that outputsa negative electrode plating efficiency. The function may be referencedor indexed via plating electrolyte pH.

The vertical axis represents negative electrolyte plating efficiency andnegative electrolyte plating efficiency increases in the direction ofthe vertical axis arrow. The horizontal axis represents platingelectrolyte pH and plating electrolyte pH increases in the direction ofthe horizontal axis arrow.

Curve 302 represents the relationship between plating electrolyte pH andnegative electrode plating efficiency, which may be referred to as thecoulombic efficiency for the negative plating reaction. In one example,curve 302 may be expressed as:Plate_(eff)=0.138·ln(pH)+0.8514where Plate_(eff) is the plating efficiency of the negative electrode,ln is the natural logarithm, and pH is the pH value of the platingelectrolyte.

In one example, the plating efficiency may be empirically determined viaadjusting the pH of the plating electrolyte and determining the platingefficiency for each pH value during charging of the iron flow electricenergy storage cell. The plating efficiency may be determined viadividing the actual weight of metal deposited to the negative electrodeduring charging of the iron flow electric energy storage cell by thetheoretical weight of metal that would be deposited to the negativeelectrode during charging of the iron flow electric energy storage cellaccording to Faraday's law.

Referring now to FIG. 4 , a plot 400 that illustrates an examplerelationship between battery SOC and open circuit voltage (OCV) at ET100is shown. ET100 represents the battery voltage measured at positive andnegative bus bars. The plot represents a function that outputs SOC for abattery. The function may be referenced or indexed via OCV (e.g.,voltage of the IFB cell or cell stack when the IFB cell or cell stack isdisconnected from external electric loads).

The vertical axis represents plating OCV and OCV increases in thedirection of the vertical axis arrow. The horizontal axis represents SOC% and SOC % increases in the direction of the horizontal axis arrow.

Curve 402 represents the relationship between SOC % and OCV. In oneexample, curve 402 may be expressed as:SOC _(OCV)=−0.518·(OCV _(ET100))²+67.098(OCV _(ET100))−2010.7where SOC_(OCV) is the battery SOC determined from OCV and OCV_(ET100)is the open circuit voltage at ET100 of the selected battery.

In one example, the SOC and OCV relationship may be empiricallydetermined via measuring the OCV and then fully discharging the batterywhile measuring the amount of charge that leaves the battery during thedischarge process. The amount of charge that exits the battery duringthe discharge process divided by theoretical amount of charge thebattery may store indicates the SOC for the particular OCV.

Referring now to FIG. 5 , a method for operating the electric energysystem as shown in FIGS. 1A and 2 is shown. The method of FIG. 5 may beincluded as executable instructions stored in non-transitory memory ofthe system of FIGS. 1A and 2 . In addition, the method of FIG. 5 maywork in cooperation with the system of FIGS. 1A and 2 to receive dataand adjust actuators of the control the system in FIGS. 1A and 2 .Further, the method of FIG. 5 may communicate with external systems inthe physical or real world via the system of FIGS. 1A and 2 . The methodof FIG. 5 describes determining SOC for individual electric energystorage device cell stacks within an electric energy storage system, butthe method described herein may be applied to an entire electric energystorage system or individual cells.

At 502, method 500 judges if operation of the electric energy storagesystem of FIGS. 1A and 2 is requested. Operation of the electric energystorage system may be requested via human input or via input from anexternal controller. If a request to operate the electric energy storagesystem has been generated, the answer is yes and method 500 proceeds to504. Otherwise, the answer is no and method 500 proceeds to 550.

At 550, method 500 deactivates electrolyte pumps (e.g., 130 and 131 ofFIG. 1A). The electrolyte pumps may be deactivated to conserve energy.Method 500 proceeds to 552.

At 552, method 500 opens the main contactor (e.g., 277 of FIG. 1A) sothat the electric energy storage system is electrically decoupled fromand electrically isolated from external electric power sources andelectric power consumers. Method 500 proceeds to exit.

At 504, method 500 activates electrolyte pumps (e.g., 130 and 131 ofFIG. 1A). The electrolyte pumps are activated to allow electrolyte toflow between storage tanks and reaction cells. Method 500 proceeds to506.

At 506, method 500 closes the individual cell stack contactors (e.g.,225-228 of FIG. 1A) so that the electric energy storage system may beelectrically coupled to an internal voltage bus within the electricenergy storage system. Method 500 proceeds to 508.

At 508, method 500 determines plating electrolyte and redox electrolytevolumes and concentrations. Plating and redox electrolyte volumes may bestored in controller memory and retrieved from controller memory.Alternatively, plating electrolyte and redox electrolyte volumes may bedetermined via level sensors. Concentrations of plating electrolytes andredox electrolytes may be determined from the amounts of additives inthe respective electrolytes. Alternatively, concentrations of therespective electrolytes may be determined via sensor output. Method 500proceeds to 510.

At 510, method 500 begins to receive charge from external power sourcesto the electric energy storage system. Alternatively, method 500 maybegin to supply charge from the electric energy storage system toexternal electric power consumers. Method 500 may begin receiving orsourcing electric power after issuing an active signal to an externalcontroller and/or via closing one or more contactors (e.g., maincontactor 277). Method 500 proceeds to 512.

At 512, method 500 determines battery cell stack current. Method 500 maydetermine current entering or exiting a particular electric energystorage cell stack (e.g., 240-246 of FIG. 2 ) via output of a currentsensor. Method 500 also determines pH of electrolyte in positive andnegative reactors via pH sensor output received to the control system.Method 500 also determines shunt current within the electric energystorage device cell stack. The shunt current may be empiricallydetermined. In one example, the shunt current in the electric energystorage cell stack may be empirically determined via measuring batterycapacity loss over idling conditions where no external current wasapplied, but all battery cells were connected via electrolyte shuntpath. Method 500 also determines ionic movement within the electricenergy storage device cell stack. The ionic movement may be empiricallydetermined. In one example, the ionic movement in the electric energystorage cell stack may be empirically determined via ex-situ measurementof electrolyte ionic concentrations via ion chromatography. Method 500proceeds to 514.

At 514, method 500 determines SOC values for the electric energy storagedevice positive and negative electrolytes via the following equations:

${SOC}_{pos} = \frac{\sum\limits_{i = 0}^{n}{\left( {\frac{{IT}\; 100}{F} - \frac{I_{s,{pos},i}}{F} - {A_{a}N_{{Fe3} +}}} \right)\Delta t_{i}}}{{V_{{pos},0}\left\lbrack {Fe^{2 +}} \right\rbrack}_{0} + {\sum\limits_{i = 0}^{n}\left\lbrack {{- \left( {N_{{Fe2} +} + N_{{Fe3} +}} \right)}A_{a}\Delta t_{i}} \right\rbrack}}$${SOC}_{neg} = \frac{\sum\limits_{i = 0}^{n}{\left( {\frac{{IT}\; 100*\eta}{2F} - \frac{I_{s,{neg},i}}{2F} - {\frac{1}{2}A_{a}N_{{Fe3} +}}} \right)\Delta\; t_{i}}}{{V_{{neg},0}\left\lbrack {Fe^{2 +}} \right\rbrack}_{0} + {\sum\limits_{i = 0}^{n}\left\lbrack {\left( {N_{{Fe2} +} + {\frac{3}{2}N_{{Fe3} +}}} \right)A_{a}\Delta\; t_{i}} \right\rbrack}}$where SOCpos is SOC based on positive electrolyte, n is the number ofsteps in the summation during the time interval in which SOC isestimated, IT100 is the total current flow through the electric energycell stack during the time interval in which SOC is estimated, F isFaraday's number, I_(s,pos,i) is the total shunt current for thepositive electrolyte during the time interval in which SOC is estimated,A_(a) is the iron flow battery system active area, N_(Fe3+) is the fluxdensity for ferric ions from the positive electrolyte to the negativeelectrolyte, Δt_(i) is the time interval between steps, V_(pos,0) is theinitial volume of the positive electrolyte, [Fe²⁺]₀ is the initialconcentration of ferrous ions in the positive and negative electrolytes,N_(Fe2+) is the flux density for ferrous ions from the positiveelectrolyte to the negative electrolyte, SOCneg is SOC based on negativeelectrolyte, η is the coulombic efficiency for the negative platingreaction, I_(s,neg,i) is the total shunt current for the negativeelectrolyte during the time interval in which SOC is estimated, andV_(neg,0) is the initial volume of the negative electrolyte. Method 500proceeds to 516.

At 516, method 500 determines the electric energy storage device cellstack SOC. During charging of the electric energy storage device cellstack, the SOC is given by:SOC=max(SOCpos,SOCneg)where max is a function that returns the greater value of argumentsSOCpos and SOCneg. During discharging of the of the electric energystorage device cell stack, the SOC is given by:SOC=min(SOCpos,SOCneg)where min is a function that returns the lesser value of argumentsSOCpos and SOCneg. These SOC values are SOC values that are based onelectrolyte. Method 500 proceeds to 518.

At 518, method 500 judges if there is a change from charging theelectric energy cell stack to discharging the electric energy cellstack, or vice-versa. If so, the answer is yes and method 500 proceedsto 520. Otherwise, method 500 returns to 502. The change in operationfrom charging to discharging, or vice-versa, provides an opportunity todetermine an open circuit voltage of the electric energy storage devicecell stack without interrupting operation of the cell stack. Asexamples, the controller may switch from charging the electric energycell stack to discharging the electric energy cell stack when a SOCincreases above an upper threshold SOC during charging. Similarly, thecontroller may switch from discharging the electric energy cell stack tocharging the electric energy cell stack when a SOC decreases below alower threshold SOC while discharging. Alternatively, a microgridcontroller may demand that the electric energy storage system to go fromdischarging to charging, or vice-versa. The upper threshold SOC andlower threshold SOC may be predetermined quantities, and may correspondto when the electric energy cell stack is charged to capacity and fullydischarged, respectively.

At 520, method 500 electrically decouples the electric energy cell stackfrom the electric power conductor 260, other cell stacks, and externalelectric power supplies and consumers for at least 30 seconds. Method500 also determines an open circuit voltage of the electric energy cellstack once the electric energy cell stack is decoupled from the electricpower conductor 260. Method 500 may decouple the electric energy cellstack via opening a contactor (e.g., contactor 225 of FIG. 2 ). Thevoltage of the electric energy storage cell stack is determined via thecontroller. Method 500 proceeds to 522.

At 522, method 500 determines the SOC_(ocv) (state of charge based onopen circuit voltage) via a function that relates SOC to open circuitvoltage of the electric energy device cell stack. An example of such afunction is illustrated in FIG. 4 . Method 500 references the functionand determines the SOC_(ocv) value. Method 500 proceeds to 524.

At 524, method 500 judges if SOC based on electrolyte is within apredetermined percentage of SOC_(OCV). In one example, if SOC determinedat 516 is within 10% of SOC_(OCV), then the answer is yes and method 500proceeds to 528. Otherwise, the answer is no and method 500 proceeds to526.

At 528, method 500 determines a SOC adjustment factor. In one example,the adjustment factor may be determined via the following equation:

${SOCAdj} = \frac{SOC}{{SOC}_{OCV}}$where SOCAdj is the SOC adjustment factor, SOC is the SOC determined at516, and SOC_(OCV) is the SOC based on OCV as determined at 522. Method500 may communicate SOC values during charging and discharging cycles toan external controller and/or a human/machine interface aftermultiplying SOC determined at 516 by SOCAdj and determining an adjustedSOC that is communicated to external devices. Method 500 returns to 502.

At 526, method 500 may perform mitigating actions to improve SOCestimates. In one example, performing mitigating actions may includerequesting and carrying out a cleansing of the electric energy storagedevice cell stack. The cleansing cycle may include fully discharging theelectric energy storage device to an external or internal load and thenmixing plating electrolyte with redox electrolyte. The electric energystorage device cell stack may be discharged via closing a contactor ofthe electric energy storage device (e.g., 225), closing the maincontactor (e.g., 277), and supplying charge to an external electric load(e.g., 278). Method 500 may also communicate the status of the electricenergy storage device cell stack to an external controller via acommunication network (e.g., LAN or WiFi). Mixing of the electrolytesduring the cleansing procedure may be performed as previously described.Method 500 returns to 502 after performing the cleansing procedure.

Thus, the method of FIG. 5 provides for a method for determining stateof charge of an electric energy storage device, comprising: adjustingoperation of an electric energy storage device via a controlleraccording to a state of charge of the electric energy storage device,the state of charge generated via a plating efficiency of the electricenergy storage device and a current flow of the electric energy storagedevice. The method includes where adjusting operation of the electricenergy storage device includes performing a cleansing cycle on theelectric energy storage device, and where generating the state of chargeincludes multiplying the plating efficiency and the current flow. Themethod includes where performing the cleansing cycle includesdischarging the electric energy storage device and mixing negativeelectrolyte with positive electrolyte. The method includes whereadjusting operation of the electrical energy storage device includescommunicating the state of charge of the electrical energy storagedevice to a controller that is external from the electrical energystorage device.

In some examples, the method includes where the state of charge of theelectrical energy storage device that is further generated viasubtracting a shunting current of the electrical energy storage devicefrom a result of multiplying the plating efficiency of the electricenergy storage device and the current flow of the electric energystorage device. The method includes where the plating efficiency isestimated via a pH level of an electrolyte of the electrical energystorage device. The method includes where the electrical energy storagedevice is an iron flow battery. The method includes where the state ofcharge generated via multiplying a plating efficiency of the electricenergy storage device and the current flow of the electric energystorage device is a state of charge for a negative electrolyte of theelectric energy storage device.

The method of FIG. 5 also provides for a method for determining state ofcharge of an electric energy storage device, comprising: adjustingoperation of an electric energy storage device via a controlleraccording to result of a comparison of a difference between a firststate of charge of the electric energy storage device that is generatedvia a plating efficiency of the electric energy storage device and athird state of charge of the electric energy storage device that isgenerated via an open circuit voltage of the electric energy storagedevice. The method further comprises generating a second state of chargeof the electric energy storage device that is generated without theplating efficiency and without the open circuit voltage. The methodincludes where the second state of charge is generated via subtracting ashunt current from a current flow of the electric energy storage device.

In some examples, the method further comprises generating a chargingstate of charge during charging of the electric energy storage devicevia selecting a greater of the first state of charge and the secondstate of charge. The method further comprises generating a dischargingstate of charge during discharging of the electric energy storage devicevia selecting a lesser of the first state of charge and the second stateof charge. The method further comprises generating a correction factorand applying the correction factor to the first state of charge when aresult of the comparison is less than a threshold value.

Note that the example control and estimation routines included hereincan be used with various power conversion system configurations. Thecontrol methods and routines disclosed herein may be stored asexecutable instructions in non-transitory memory and may be carried outby the control system including the controller in combination with thevarious sensors, actuators, and other system hardware. The specificroutines described herein may represent one or more of any number ofprocessing strategies such as event-driven, interrupt-driven,multi-tasking, multi-threading, and the like. As such, various actions,operations, and/or functions illustrated may be performed in thesequence illustrated, in parallel, or in some cases omitted. Likewise,the order of processing is not necessarily required to achieve thefeatures and advantages of the example embodiments described herein, butis provided for ease of illustration and description. One or more of theillustrated actions, operations and/or functions may be repeatedlyperformed depending on the particular strategy being used. Further, atleast a portion of the described actions, operations and/or functionsmay graphically represent code to be programmed into non-transitorymemory of the computer readable storage medium in the control system.The control actions may also transform the operating state of one ormore sensors or actuators in the physical world when the describedactions are carried out by executing the instructions in a systemincluding the various described hardware components in combination withone or more controllers.

This concludes the description. The reading of it by those skilled inthe art would bring to mind many alterations and modifications withoutdeparting from the spirit and the scope of the description. For example,different components within the power system may be electrically coupledto earth ground and the first and second electrolytes to reduceelectrical potentials between an electric power system and earth ground.

The invention claimed is:
 1. A method, comprising: operating an all-ironredox flow battery to generate a state of charge; and adjusting, with anelectronic control system having instructions stored therein, operationof the flow battery according to the state of charge, the state ofcharge determined based on a parameter indicative of plating efficiencyat a negative electrode, the parameter further indicating the flowbattery's capacity to source and sink current.
 2. The method of claim 1,where adjusting operation of the flow battery includes performing acleansing cycle on the flow battery.
 3. The method of claim 1, where theflow battery includes a tank storing a plating electrolyte.
 4. Themethod of claim 2, where performing the cleansing cycle includesdischarging the flow battery and mixing negative electrolyte withpositive electrolyte.
 5. The method of claim 1, where the state ofcharge is further determined based on subtracting a shunting current ofthe flow battery from a result of multiplying plating efficiency and thecurrent flow.
 6. The method of claim 1, where the plating efficiency isbased on a pH level of an electrolyte of the flow battery.
 7. The methodof claim 1, where the flow battery is responsive to a microgridcontroller.
 8. The method of claim 1, wherein the flow battery includesa plating electrolyte tank and a redox electrolyte tank, where both theplating electrolyte and the redox electrolyte use a same salt atdifferent molar concentrations.
 9. A method for determining state ofcharge of an iron flow battery, comprising: adjusting operation of theiron flow battery via a controller according to a result of a comparisonof a difference between a first state of charge of the iron flow batterythat is determined based on a calculation with a plating efficiency ofthe iron flow battery and a third state of charge of the iron flowbattery that is determined based on an open circuit voltage of the ironflow battery, where the iron flow battery includes a plating electrolytetank and a redox electrolyte tank.
 10. The method of claim 9, furthercomprising determining a second state of charge of the iron flow batterythat is determined without the plating efficiency, where both a platingelectrolyte and a redox electrolyte use a same salt at different molarconcentrations.
 11. The method of claim 10, where the second state ofcharge is determined based on subtracting a shunt current from a currentflow of the iron flow battery.
 12. The method of claim 11, furthercomprising determining a charging state of charge during charging of theelectric energy storage device iron flow battery based on selecting agreater of the first state of charge and the second state of charge. 13.The method of claim 12, further comprising determining a dischargingstate of charge during discharging of the iron flow battery based onselecting a lesser of the first state of charge and the second state ofcharge.
 14. The method of claim 9, further comprising_determining acorrection factor and applying the correction factor to the first stateof charge when a result of the comparison is a difference that isgreater than a predetermined percentage of the third state of charge.15. An electric power system, comprising: an iron flow electric energystorage cell stack including a positive electrode and a negativeelectrode, the positive electrode in physical communication with a firstelectrolyte that is stored in a first tank of the system and thenegative electrode in physical communication with a second electrolytethat is stored in a second tank of the system; and a controllerincluding executable instructions stored in non-transitory memory todetermine a first state of charge based on a plating efficiency and todetermine a second state of charge from other than the platingefficiency, and instructions to determine a charging state of charge byselecting a greater of the first state of charge and the second state ofcharge during charging of the iron flow electric energy storage cellstack.
 16. The electric power system of claim 15, further comprisingadditional instructions to determine a discharging state of charge basedon selecting a lesser of the first state of charge and the second stateof charge during discharging of the iron flow electric energy storagecell stack.
 17. The electric power system of claim 16, furthercomprising additional instructions to multiply the plating efficiencyand current of the iron flow electric energy storage cell stack.
 18. Theelectric power system of claim 15, further comprising additionalinstructions to determine a correction factor from the charging state ofcharge and an open circuit state of charge estimate.
 19. The electricpower system of claim 18, further comprising additional instructions tomultiply the correction factor and the charging state of charge.
 20. Theelectric power system of claim 15, where the iron flow electric energystorage cell stack includes a membrane that physically separates andisolates the first electrolyte from the second electrolyte.